TW200909500A - Barium sulfate-containing composite (1) - Google Patents

Abstract

The invention relates to a barium sulfate-containing composite, a production method thereof and an application thereof. The titanium dioxide-containing composite is composed of a filler and pigments dispersed in a polymer matrix, wherein the composite contains at least one thermoplastic plastic, a high power plastic and/or an epoxy resin, wherein the crystal size of titanium dioxide (d.sub.50) is smaller than 350 nanometers, and preferably smaller than 200 nanometers, more preferably between 3-50 nanometers and the barium sulfate may be surface modified through inorganic and/ or organic means.

Description

200909500 IX. Description of the invention: [Technical field to which the invention pertains] The method for producing the same, and the invention relates to a composite containing barium sulfate, the use thereof. [Prior Art] In the polymer system, the use of conventional fillers and pigments (also known as additives) is known to be the type of exchange between the particles of the filler or pigment and the matrix. And the intensity will affect the nature of the Komposit. By modifying the surface according to the standard (__=, the exchange effect between the particles and the polymer matrix can be changed, and the system r composed of the filler and the pigment in a polymer matrix is also called) I complex") (4) quality change. A conventional method of surface modification is to functionalize the surface of the particles using an alkoxyalkyl decane. This surface modification can be used to improve the compatibility of the particles with the parent material. Further, the particles may be bonded to the substance by appropriately selecting a functional group. The disadvantage of using such a conventional filler is that the filler causes a large scattering of visible light due to its particle size and thus greatly reduces the transparency of the composite. In addition, for many applications, the conventional chemical filler D such as calcium carbonate has poor chemical resistance and is also a disadvantage. A second possible way to improve the mechanical properties of the polymeric material, the use of ultra-thin (uUrafein) particles. US patent us side, 667, 36 〇 reveals that the polymer composite contains 50% by weight of nano particles, and the nanoparticles of the particles proposed by the 100' Ding "card" are: metal oxide, metal arm

Compounds, metal nitrides, and it is difficult to be a few times. „ ^ J,L 隹 is a bismuth compound, metal fluoride, and metal gas 6 200909500 compound, in which the belly grain of the early 131-1000 surface has not been modified. The parent material is epoxy resin, «acid _ 1 likang, concentrating, concentrating, polyene, synthetic rubber, polyamino carboxylic acid, polyphenylene, polyphenylene, oxide, polyketone, And its octamers are combined with this. Us_3_6 6,667, the composites mentioned have better mechanical properties, in particular tensile properties and tensile strength, compared to unfilled polymers. The disadvantage of the above ultrafine particles is that it tends to have a high Mohs hardness, so that it has a great effect on the wound. In addition, the folding of the material

The index (for example, two fi /μ # _<), , , L - titanium telluride n = 2.7) is much better than the refractive index of the polymer material. This makes the light scattering effect stronger and thus reduces the transparency of the composite. A special case in typical pigments and fillers is the sulfuric acid lock (BaS04) ^ ^ 钡壬 chemically inert ' and does not react with typical polymers. The Mohs's hardness of barium sulfate is soft, so the Mohs hardness of titanium dioxide is about 6.5 in "rutile modification". Barium sulfate has a small refractive index, η = 1.64. German Patent Application No. DE 10 2005 025 719 A1 discloses a method for the application of disintegrated barium sulfate (average particle size 5G5_), which is applied with a dispersing agent, which is processed into a plastic precursor (v〇). Rstufe) ^ such as polyol). In this method, a plastic is produced which comprises a dispersing agent and a disintegrating (de-agglomerated) barium sulfate containing a crystallization inhibitor. International Patent WO 2QG7_〇39〇25 A1 mentions the use of barium sulphate or carbonic acid (tetra) in a transparent polymer which contains at least one organic component. In the case of such disintegrated barium sulfate particles coated with an organic substance, a general disadvantage is that the organic component is not widely used. Particularly disadvantageous is the use of knots 200909500: formulations because they have been used in the manufacture (deposition) of barium sulfate particles. The crystallization inhibitor is compatible with the plastic precursor or plastic: it limits the possibility of use of this product. In extreme cases, this means that a new product has to be developed and manufactured for all kinds of plastics. 039二1Γ Μ200·Mountain 719 A1 application and the particle size distribution of the other-sized particles of the disintegrated barium sulfate particles described in W〇2〇〇7_1, whose average particle size is less than 2 And should be: 250 nm 'Ultra> < 2GG nanometer, more suitable for Xiannai, special < 100 to win this (four) secondary particle distribution caused by dust flying (four) to a large m for safety 'especially in super In the case of fine particles, this dusty situation should be avoided. Another disadvantage of the filler-modified composite described in this prior art is that its mechanical properties are insufficient for many applications. SUMMARY OF THE INVENTION The object of the present invention is to overcome the disadvantages of the prior art. In particular, it is an object of the present invention to provide a composite which has a much better flexural modulus (bending strength, tensile modulus, tensile strength, tear resistance, etc.) than prior art composites. Resistance to rupture, anti-strike and low wear. This is especially important for certain applications of composites, such as in the automotive, aircraft or space sectors. Therefore, 'in sliding bearings, gears, or rollers and pistons. The layer is expected to have a low wear rate. Some components have a long life and make the machine life longer. In synthetic fibers (for example, those made of PA6, PA66 or PET), the tear strength can be changed to 1. 200909500 The purpose of thinking can be achieved by using the composite of the invention with the patent application:: point. The characteristics of the preferred step-by-step can be found in the scope of the patent scope of J. The brother Yu Shen is unexpectedly according to the invention' When using the deposited barium sulfate of the crystal size d50 less than 350 broadly measured by the Debye-Scherrer method, the mechanical properties and the properties of the polymer composite have been greatly improved. This is even more alarming because the sulfate-locking particles that have not been surface-modified do not create a bond between the grain: and the mother. In the prior art, the 1::::: between the additive and the parent f improves the mechanical properties and friction properties of the composite:: Particle 2: 纟# In other embodiments, provided and used The barium sulfate, the sub-establishment of the combination. To provide acid bismuth particles in accordance with the present invention. However, the required surface-to-mass bonding is adjusted according to the standard. (The lanthanide system is used to treat the particles and the mother after (for example, after the water-based mediation sink == is applied after the barium sulfate particles are produced. —Additional method steps. This process: square:::The advantage of quality operation is that the possible large variation mode m1 Φ can make the effect of the formation of barium sulfate in the case of sedimentation. Negative by the sediment ~ 丄: Another aspect is easier to control the size and shape of the sulphuric acid lock particles. The method of the sulphuric acid lock used in the present invention is implemented by the method of "bar" " The barium sulphate used in the Saki rice grade is used to treat several kinds of reactants (such as in the manufacturer, for example, in air yttria or lanthanum sulphide or cesium chloride water soluble 200909500 liquid and sodium sulfate or sulfuric acid). In the present invention, the barium sulfate is preferably in the form of a sediment suspension after deposition. The barium sulfate used in the present invention is firstly swelled, and the wastewater thus produced does not contain organic matter. Contaminant. At this time, the sulfur 酴卞 &quo t; claw 钡 is in the form of a concentrated barium sulfate suspension. f can be sprayed and dried according to the drying method, the milling operation can be dried by the conventional dry sulphuric acid sulphate suspension for drying, and / Or the powder drying method is achieved. The dry powder may have to be subjected to the subsequent milling operation. The method is carried out. To manufacture the composite of the present invention, they have the advantages that the coarser particles have less dust and are easy to flow. Preferably, spray-dried barium sulphate powder is used to spray the condensate of the dryer to form ash. The powder is surprisingly dispersible. The composite of the present invention comprises a polymer matrix having a deposition of 0.1 to 60% by weight. The barium sulfate particles have an average crystal size of less than 35 nanometers (measured by the Debye-Scherrer method). The crystal size is seven. It is preferably less than the class ' and is 3 50 nanometers. Here, according to the invention, the barium sulfate The particles may be surface-modified or 'surface-free.' In addition, the composite of the present invention may contain conventional ingredients conventionally used by experts, such as mineral fillers, glass fibers, stabilizers, and procedures. (also known as "protection system"), such as dispersing aids, separating agents 'antioxidants, anti-separation agents, etc.), pigments, anti-flame agents (such as hydrazine, antimony trioxide, hydrogen emulsified magnesium, etc.) Vulcanization accelerator, vulcanization slowing agent, zinc oxide, stearic acid, sulfur, peroxide/softener. 200909500 By way of example, the composite of the invention may additionally contain up to 80% by weight. (and preferably 1〇~80% by weight) of mineral fillers and/or glass fibers, up to 10% by weight (and preferably 〜5~1〇% by weight) of stabilizers and process additives (eg dispersion aids) , a separating agent, an antioxidant, etc.), a pigment which is as much as 丨〇 里 里, and an anti-flame agent (for example, aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.) up to 4% by weight. For example, the composite of the present invention may contain 〇丨~6〇% by weight of titanium dioxide 〇 heavy table% mineral filler and/or glass fiber, 〇〇5~j〇% by weight of stabilizer and program additive ( For example, a dispersion aid, a separating agent, a turmeric agent, etc.), 〇~1 〇% by weight of a pigment, 〇~40% by weight of an antifogging agent (for example, bismuth alumina, antimony trioxide, magnesium hydroxide, etc.). 〆X Bin. The material or the parent material may be a thermoplastic plastic, a high-power plastic 2 ¥ reading grease composition. Suitable examples of thermoplastic materials are polystyrene PET, polyethylene, polypropylene, polystyrene, their totals and mixtures, and mersole's merchant PMMA $polyvinyl chloride. High-power plastics \, tweezers have PTFE, fluorine thermoplastics (such as FEP, PFA, etc.), crystal poly F characters, such as PES, PSU, PPSU, etc.) polyether melamine, liquid: and polyether ketone. Further, an epoxy resin is suitable as a polymer matrix. The mute compound can contain barium sulphate, 〇~80::0 heavy Dong% of the surface of the deposit is changed 〇.〇5~10 heavy Θ. ~ 重里% mineral fillers and / or glass fiber, separation agent, household _ 垔 / ° female prescription and process additives (such as dispersion subsidies, a few oxidants, etc.), 〇 ~ flame agent (such as , :: '0 ~ 40% by weight of the fire-resistant polymer or parent material ^ wind oxidation town, etc.). The shell is made of a thermoplastic plastic, a high-power plastic 200909500 or an epoxy resin. Suitable examples of esters, polyamides, PET, thermoplastic materials are poly

B 曰 polymer, and polyether ketone. Further, an epoxy resin is suitable as a polymer matrix. According to the present invention, particles of ultrafine barium sulfate which have not been surface-modified can be used. If this is not the case, in a particular embodiment, the barium sulfate particles may have an inorganic and/or organic surface modification. A typical example of the inorganic surface modified portion of the ultrafine barium sulfate is a compound containing at least two of the following elements: aluminum, lanthanum, cerium, calcium, lanthanum, gas, cobalt, iron, phosphorus, manganese, oxygen, sulfur, Niobium, nitrogen, strontium, vanadium, zinc, tin, and/or wrong compounds or salts such as sodium citrate, sodium aluminate and aluminum sulfate. The inorganic surface treatment of the ultrafine sulfuric acid lock is carried out in an aqueous sludge. Here, the reaction temperature is preferably not more than 5 〇 t:. The pH of the suspension, for example, is adjusted to a pH greater than 9 when NaOH is used. Then, after vigorous stirring, the post-treatment chemical (inorganic compound) is added to 'it is preferably an inorganic water-soluble compound, for example, aluminum, ruthenium, ruthenium, osmium, gas, cobalt, iron, phosphorus, carbon, manganese, oxygen. a compound or salt of sulfur, antimony, nitrogen, antimony, vanadium, zinc, tin and/or antimony. According to the present invention, the pH and amount of the treatment chemical thereafter are selected such that the chemical is completely dissolved in water. . The suspension is intensively mixed' so that the post-treatment chemicals are evenly distributed in the suspension and should be disturbed for at least 5 minutes. In the next step, the pH of the suspension/liter solution is lowered. Here, an advantageous method is to slowly lower the pH value by 12 200909500 (four) (four). It is particularly advantageous to lower the pH value within 1 〇 to 9 〇: to a pH value of 5 to 8'. It is then a time for the teacher to be about i hours of ripening. No more than (10) here. This aqueous suspension is then washed and dried. To dry this ^,, dry can be carried out by spray drying, freeze-drying, and islanding procedures. After the Ik of the dried powder is ground, the milling operation can be carried out by a conventional method. To produce (4) the ultra-fine surface modification of the known particles, the water-based BaS04 suspension (which is composed of 从p, wind &;; Ba has been made of inorganic surface modified BaS 〇 4 particles) in addition to at least A Shi Xi burn modified. The (four) used is preferably an alkoxyalkyl sulphide. The oxylated base stone is preferably selected from the group consisting of: octyl triethoxy sulphur, r-methyl propyl decyl propyl trimethoxy sulphur, / _ glycidyl propyl trimethoxy decane , r aminopropyl triethane decane, r-aminopropyl trimethoxy ketone, isocyanate propyl triethoxy sulphur, ethylene trimethoxy sulphur and/or chlorination Money, such as the plant aminopropyl stone eve half (four) burning (Fa·GE). For this reason, a Bas0J float composed of a surface-modified Bas04 particle is subjected to a strong adsorption or dispersion and a seed-like oxylate appearance before or after the cleaning. Then according to this: Ming: the period of ripening, preferably 10 to 60 minutes of ripening time, should be at a maximum of 4 (TC temperature. Then continue as described above. If you do not use this method, you can also dry this The alkoxyalkyl decane is applied to the inorganic modified particles by mixing. According to the invention, the following compounds are particularly suitable as organic surface modifiers.· Polyether, decane, polyoxyalkylene, polycarboxylic acid, fatty acid, polyethylene Ethylene glycol, 13 200909500 polyester, polyamine, polyalcohol, organic phosphonic acid, titanate, acid salt, alkyl and / or aryl sulfonate, alkyl and / or aryl sulfate, alkane And / or aryl phosphate. &amp; * The surface modification of titanium dioxide can be carried out according to a conventional method. According to the present invention, the barium sulfate suspension reacts with a bismuth component, thereby causing enthalpy of use. The cerium component may be various water-soluble cerium compounds such as cerium lanthanum chloride and cerium hydroxide. The cerium ions are adsorbed on the surface of the cerium sulfate particles, and then the appropriate organic compound is added thereto under strong agitation or at the time of dispersion. In suspension, organic compounds are selected It forms a difficult/combination with cerium ions. The organic compound is deposited on the surface of barium sulphate with an excess of cerium ions by adding an organic compound to the sulphuric acid pin suspension. Suitable organic compounds are listed below. Selected as: alkyl and/or aryl sulfonate, alkyl and/or aryl sulfate, alkyl and/or aryl phosphate or a mixture of at least two of these compounds, wherein the alkyl or group The radical may be substituted by a functional group. The organic compound may also be a fatty acid, which may be functional, or a mixture of at least two of these compounds may be used. For example, the following may be used: calcined acid salt, polyethyl b Sodium, sodium sulfonate, sodium polystyrene sulfonate, sodium dodecyl benzene sulfonate, laurel S & sodium sulfate, sodium citrate sulfate, hydroxylamine sulfate, triethanol ammonium lauryl Sulfate, monoethyl monobasic phosphate, lithium peroxyoctane sulfonate, 12-bromo-1-dodecanesulfonic acid, sodium 10-hydroxysodium sulfonate, sodium staghorn phthalate, 10- Sodium hydrosulfide-1-hexadecane sulfonate, 16-hexadecane (1), sodium sulfate, oil lanthanum Hexyl alcohol sulphate oleic acid sulphate, 9,1 〇-dihydroxystearic acid, 14 200909500 Iso-acidic acid, stearic acid, oleic acid. β Hai organically modified barium sulphate can be directly saved 5 Use, or use n directly to form a water-like paste. The drying operation can be carried out by conventional methods. For (4), special limb materials (4) machine, drying: machine: dryer and / or pulse drying Machine, but according to the invention also =, his dryer "depending on the drying method, the dry milling operation can be achieved by the conventional method: the average particle size of the page grinding such as 钡 should be d 1 = machine surface modification Sulfuric acid, human Ding and d5 〇-1 Nai water ~ 100 nm. And should be d5 〇 = 1: rice Ι μιη, especially suitable d5 〇 = 5 nm ~ 〇 5_ ' and should be dispersed to the primary before organic modification Particle size. The primary particle size should have a logarithmic particle size distribution, the median value of the basin is ~5000 nm, and the d = 1~1 〇〇〇 nanometer, especially the d=5~5 〇〇 nanometer' geometric standard The deviation σ § &lt; 1.5, and preferably ^ &lt; The organically modified barium sulfate may be further post-treated with a functional decane derivative or a functional decane after organic modification. For example, butyl triethoxy decane, methyl triethoxy decane, methacryloxypropyl methoxy decane, glycidoxypropyl trimethoxy decane, amine group can be used. Propyltriethoxydecane, r-isocyanatopropyltriethoxydecane, vinyltrimethoxydecane. According to the present invention, the β-surface-modified sulfuric acid-based particles may optionally have one or more functional groups, such as _ or several hydroxyl groups, amine groups, carbonyl groups, epoxy groups, vinyl groups, methacrylates. / and or isocyanate, sulfuric acid, alkyl thiocarboxylate, di- and / or polysulfide. The surface modifier can be chemically and/or physically bonded to the particle surface 15 200909500. The chemical combination is either covalent or ionic. The physical combination can be a bipolar bipolar bond or a van der Waals force combination. The combination of surface modifiers should be achieved via a combination of valence or physical bipolar-bipolar bonding. According to the present invention, the surface-modified barium sulfate particles can be modified by surface modification to be partially and completely chemically and/or physically bonded to the chemically bonded chemically to be covalently and ionically bonded. The applicable physical combination is a combination of bipolar-bipolar and van der Valli. To produce the composite of the present invention, it is preferred to first produce a Master Batch, which preferably contains 5 to 8 G weight percent barium sulfate. This master batch can then be diluted with only (iv) green polymer or mixed with other components of the receptor (Rezeptur) and dispersed again if necessary. A method can also be used to make the composite of the present invention, wherein the titanium dioxide is first processed and dispersed in the organic material 'especially in the polyol, polyethylene glycol, poly-inspection, poly-and acid and its derivatives, ah salt, B Internal amine, stone worm, vinegar, vinegar, cellulose, styrene, methyl acetonate, organic dimethyl amide, epoxy resin or softener (such as reading, deputy p, (10) m. These organic substances which interact with barium sulphate can then be used as a starting material to make a composite. To disperse barium sulphate in the main batch or organic material, a general dispersion method can be used, in particular the use of a melt. Extrusion machine, dissolver, three-roller machine, price ball, ball mill, bead mill, dipping mill, super sound = or kneading machine. Particularly advantageous is the use of dipping mill or bead mill (bead diameter d &lt; 1.5mm). The composite of the present invention has surprisingly excellent mechanical properties and friction properties. Compared with unfilled polymers, the composite of the present invention has significantly improved flexural modulus, flexural strength, and tensile strength. Modulus, tensile strength , tear resistance, fracture toughness, impact toughness, and low wear rate. [Details of the subject matter of the invention] A composite, at least a power plastic and/or at least one epoxy resin and a deposited surface modification $ The sulphuric acid lock constitutes 'the crystal size 乜 is less than 35 〇 nanometer, and is preferably smaller than the hired nanometer, especially between 3 and 50 nanometers' and the titanium dioxide can be surface-modified by inorganic and/or organic means (hereinafter also referred to as , titanium dioxide composite; --- barium sulfate complex, wherein the selected thermoplastic is at least one polyglycol, one polyamine, one kind of ethylene, polypropylene, polyphenylene, its copolymer And/or a mixture, a polycarboxylate, a hydrazine and/or a polyvinyl chloride, a bismuth sulfate complex, wherein the selected high-power plastic is at least one ΡΤΕΕ, ^ plastic plastic kick (eg FEP, PFA, etc.), PVDF, a polysulfone (such as pEs, MU, PPSu, etc.), polyetherimide, liquid crystal polymer and or polyacetate. A barium sulfate complex, which uses an epoxy resin; Ruthenium complex The composition contains 12~99.8% by weight of thermoplastic plastic, 〇1~6〇: amount. Titanium dioxide, 0~80% by weight of mineral filler and/or glass fiber/.〇6~10% by weight of antioxidant, 0~ 〇2〇% by weight of organic metal in addition to fish mites, 0~2.0% by weight of program additives (such as dispersion subsidies, 赋 赋 赋 〇 〇 H H H H H H H H H H H H H H 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 17 200909500 Such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, etc.) - a barium sulfate complex, wherein the composite contains 12~99_8 wt% high-power plastic, 〇1~6〇 weight $% barium sulfate, strontium ～80% by weight of mineral filler and/or glass fiber, 〇~5. 〇% by weight of program additives (such as dispersion aid, adhesion agent), 〇~1 〇% by weight of pigment; a composite wherein the composite contains 20 to 99.9% by weight of epoxy resin, 〇1 to 6 〇 heavy summer 钡 barium sulfate, 0 to 80% by weight of mineral filler and/or glass fiber, 〇 10% by weight of the program added Material, 〇~1〇% by weight of pigment and 〇~4〇wt〇/0 aluminum hydroxide. - a barium sulfate complex, wherein the proportion of barium sulfate in the complex is from 0.1 to 60 weight. /〇, and should be 〇. 5~ 30% by weight, especially 1. 〇~20% by weight. - a kind of barium sulfate complex 'where the titanium dioxide has an inorganic / or organic surface modifying layer; -- a kind of titanium dioxide complex ' wherein the inorganic surface modifying layer of the ultrafine titanium dioxide is composed of a compound, A compound or a salt containing at least two elements: aluminum, lanthanum, cerium, calcium, lanthanum, gas, cobalt, iron, phosphorus, carbon, manganese, oxygen, sulfur, lanthanum, nitrogen, lithium, vanadium, zinc, tin, and / or wrong; - a barium sulfate complex 'where the organic surface modifying layer is composed of one or more of the following components: decane, decane, polyoxyalkylene, polycarboxylic acid, polyester, polyether, polyfluorene Amine, polyether glycol, polyalcohol, fatty acid (and preferably 18 200909500 is an unsaturated fatty acid), polyacrylate, organic phosphoric acid, titanate, decanoic acid, alkyl and / or aryl sulfonate, alkane Base and / or aryl sulfate, alkyl and / or aryl vinegar. a barium sulfate complex wherein the surface modification comprises one or more of the following functional groups: a hydroxyl group, an amine group, a carbonyl group, an epoxy group, a vinyl group, a methacrylate group, and/or an isocyanate group, Mercaptan, alkylthiocarboxylate, di- or polysulfide. a barium sulfate complex, wherein the surface modifying layer is covalently bonded to the surface of the particle; the barium sulfate complex 'where the surface modifying layer is ionically bonded to the particle surface; the barium sulfate complex, wherein The surface modifying layer is bonded to the surface of the particle by physical exchange; - a barium sulfate complex, wherein the surface modifying layer is bonded to the particle surface with a van der Waals force; - a barium sulfate complex 'where the surface The modified layer is bonded to the polymer matrix; - a barium sulfate complex in which the titanium dioxide particles are chemically bonded to the polymer matrix, which are covalently and/or ionically bonded; ^ - a barium sulfate complex, Wherein the chemical bond between the titanium dioxide particles and the polymer matrix is covalent and/or ionic bonding; - a barium sulfate complex in which the titanium dioxide particles are physically bonded to the polymer matrix; - a barium sulfate complex The physical bond between the titanium dioxide particles and the polymer matrix 19 200909500 is a bipolar-bipolar junction (Keeson), induced bipolar-bipolar junction (Debye) or fraction. Type combination (van der Waals force). - a barium sulfate complex in which there is a physical and chemical bond between the titanium dioxide particles and the polymer matrix; - a method of producing the sulfuric acid lock complex; - a method of producing a barium sulfate complex, wherein The titanium dioxide and a portion of the green polymer are produced in a main batch, and the composite is obtained by diluting the main batch with the main polymer, wherein the main batch contains 5 to 80% by weight of barium sulfate, and preferably a method of producing a barium sulfate complex; wherein the main batch containing barium sulfate is diluted with a green polymer in the case of dispersion; - a method of producing a barium sulfate complex, wherein The main batch is mixed with the other components of the acceptor in one or several steps, and then further dispersed; \"the method of preparing the barium sulfate complex, wherein the barium sulfate is first processed and dispersed in the organic substance Medium, especially in polyols, polyethylene glycols, polyphonic, di(tetra), and derivatives thereof, AH oxime, caprolactam, sulphonic acid, squaric acid, succinic acid, cellulose, styrene Methyl acetoacetate methyl vinegar Monoamine, epoxy resin and softener (such as DOP, DIDP, DINP), wherein the sulfuric acid lock can be surface modified or not surface modified by inorganic or organic means; - a method for producing a barium sulfate complex, Wherein the organic substance acting on barium sulfate is used as a starting material to produce the composite; 20 200909500 - a method for producing a niobium m of a barium sulfate complex, wherein the barium sulfate is dispersed in a general organic matter, In particular, the use of Luo shouting machine, dissolution machine, three, one, one, machine, ball mill, bead mill, sub-mill, ultrasonic or kneading machine; - the manufacture of barium sulfate complexes * The method, which should be used to dip the mill or the beaded Weifang to disperse the barium sulfate; - to make the barium sulfate complex of the Gans - you m stone to death, and the use of the bead mill will be especially suitable for d&lt ; G.3mm; is 仏Hm, and should be d<1.〇mm, the friction property of the yttrium sulphate complex; 匕/, improved mechanical properties and improvement-manufacturing of barium sulfate complex, &amp; Make the Qin particles improve strength and flexibility at the same time One of the oxidized: cerium sulfate complex, observed in the strength and labor test of the sputum or tensile test; * bowing - sulphate lock compound, eg + hu + has improved resistance to impact toughness and / Or improved resistance to notch impact toughness; 4 Hanwu's wear resistance is improved by using the surface modified ~ barium sulfate composite present particles; with improved scratch resistance; improved tensile tear resistance ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; For the production of injection molding - barium sulfate composite ~ barium sulfate complex - barium sulfate complex 21 200909500 parts, blow molding or fiber; - the use of the barium sulfate complex to fiber form, it should have better tear strength Characteristics, the application of the barium sulfate complex, in the construction of automotive, aerospace or space navigation, in particular in the form of a plain bearing 'gear, roller or piston coating; the barium sulfate complex Application, for example Made by casting method 1, 'as a dose' as an industrial floor, as a concrete coating, when it is a soil G complement 'as a corrosion-resistant sheath to cast electrical components or other items to make metal pipes Sanitary treatment, as a carrier material in plastic, or as a storage tank for wood; The present invention is illustrated by the following examples, but the scope is not limited thereto. [Examples] [Example 1] The starting material used was a deposited barium sulfate having a crystal size d50 of 2 Å. The polymer matrix used was a commercially available epoxy resin A19_30 from the manufacturer Leuna_Harze GmbH. The hardener used was the amine hardener Ηγ 2954 from the manufacturer ν&amp;η^〇 GmbH &amp; Co·KG. The powdery barium sulfate was dispersed into a liquid epoxy resin by a dissolver (Diss〇lver), and its content was 14% by volume. After pre-dispersion, it was mixed. The material was dispersed by a dipping mill at 25 rpm for 9 minutes. The beads used were 1 mm zirconia beads. This material was mixed with a pure resin. Therefore, after the addition of the hardener, the resulting composite contains 2 to 1 volume. /. Barium sulfate. This composite hardens in a dry box. 22 200909500 In order to mechanically test this composite, a test body of a certain size was produced. The test of the fracture toughness Klc (according to ASTM E399-90) is based on the test speed 〇 lmm/knife using a tight tension [Compact Tension (TC)] specimen. In the specimen, a controlled impact 4 of a scraping blade (Rasierklinge) becomes a distinct crack. Thus, a flat stretch condition required to obtain a critical stress density factor is generated on the crack peak. The mechanical properties are tested in a three-point bending test according to DIN en ISO i78. These specimens are machined from a cast plate with a precision saw. The specimens of the five dimensions 80mmxl〇mmx4mm are tested at a speed of 2mm/ The test was carried out at room temperature. Figure 1 shows the fracture toughness of the composite as a function of barium sulfate content. The figure shows that when the concentration is 10% by volume, the rupture toughness is increased by 66% compared to the pure resin. Figures 2 and 3 show the results of the three-point bending test of the composite for barium sulfate use/indentation. The flexural modulus was raised from 267 MPa to 3509 MPa due to the use of barium sulfate. The flexural strength can be increased from 129 Mpa of pure resin to 136 MPa of 1% by volume of barium sulfate. The comparative (control) sample (which contains 5 volumes/〇 of undispersed barium sulfate) has a lower bending strength than the pure resin. To determine the ratio of the composite wear rate, the test body was sawn to a size of 4 x 4 x 20 mm3. This test body was expressed by friction using the model test device ''m〇ck und Rlng''. The compression pressure used was 〇·6 MPa, the relative speed was 0.03 m/s, and the average particle size for the solid surface was 22 μηι. Among them, the specific wear rate of the composite at 1 vol% is only 23 200909500 〇, 36 mm 3 /Nm. The specific wear rate of the pure resin is much higher 0.48 mm 3 /Nm. [Example 2] The starting material used is a surface. The modified barium sulfate has a crystal size of 5 〇 of 26 nm. The surface of the sulfuric acid lock is used as an inorganic post-treatment and a burnt-in. The inorganic surface modification is composed of a mono-aluminum oxy-compound. _ Glycidyloxypropyl trimethoxy sulfonate (Siliquest A-187 from ge silicons). This inorganic post-treatment and surface-modified barium sulphate can be produced by the following method: A 3.7 kg of a 6.5 wt% super The fine titanium dioxide particles, /, the average primary particle diameter dw is 26 nm (the result of the TEM study), and the crucible is heated to a temperature of 4 ° C under stirring, and the suspension is adjusted by using 1 〇〇 / caustic soda. pH to 12. In With vigorous stirring, 14.7mi of an aqueous sodium citrate solution (284g Si〇2/L), 519ml of aluminum sulfate solution (75g Al2〇3/L) and 9.7ml of sodium aluminate solution (275)克Al2〇3 / liter) is added to the suspension while maintaining the pH = 12.0, and the suspension is homogenized for another 1 minute with vigorous stirring. Then the pH is slowly (and preferably at 6 〇) Internal) was adjusted to pH = 7 by adding 5% sulfuric acid. Then it was aged at 4 ° C for 1 〇 minutes, and the reaction suspension was washed with water to a conductivity of less than 100 pS / cm. The washed suspension was used. The VE water was adjusted to disperse into a suspension, adjusted to a solids content of 2% by weight with VE water and dispersed by a dissolver for 15 minutes. The suspension was slowly added with 15 g of _glycidyloxy (GE Silicons). Siliquest Α-187) was dispersed by a dissolving machine. The suspension was then redispersed with the dissolving machine for 2 Torr and dried in a spray 24 200909500 dryer. Using Leuna-Harze's commercially available epoxy resin Epil〇x A19_03 Used as a polymer matrix. Using the amine hardener HY 2954 from Vantico GmbH uc〇KG The first step is to disperse the powdered barium sulphate into a liquid epoxy resin with a dissolver. The content of the bismuth sulfate is 14% by volume. After pre-dispersion, the mixture is dispersed by a dipping mill at 250 rpm. () The beads used were 1 mm dioxa beads. This material was mixed with a neat resin, so that after the addition of hardening 4, the resulting composite 纟 5 vol% sulfuric acid pin. This composite hardens in a dry box. - Similar to the above Example 1, a test body of a certain size was produced which was measured in the bending test and in terms of its fracture toughness. The results of the bending test and the fracture toughness of the composite were shown in the table and compared with the results of the composite of Example 1. The resin and the pure tree filled with 5% by volume of the surface-modified barium sulfate greatly improved the bending modulus and the bending strength was remarkably improved. And the rupture property can be significantly improved by using surface-modified barium sulfate. Compared with the barium sulfate-filled resin of Example i of 5 vol / 〇, the resin filled with 5% by volume of the double-lit barium sulfate has a marked increase in flexural modulus and bending and flexural strength. 25 200909500 __]: bending test and fracture toughness, the result of the sample acuity / person ^ &lt; hand knife edge bending modulus [MPal knot; bending strength 1 1 η fracture toughness TMpamK] pure resin (Hpilox A 19- 03) 2670 130 0.71 pure resin + 5 volumes. / 〇 钡 钡 实例 (Example 1) 2963 139 0.93 pure resin + 5 vol% surface modified barium sulfate (Example 2) 3345 148 ---- 0.76 Figure 1: The fracture toughness of the composite of Example 1 (for filling) The number of degrees). Figure 2: Flexural modulus of the composite of Example 1 (number of turns for filling) Figure 3: Flexural strength of the composite of Example 1 (the number of fillings for the degree of filling) [Example 3] The starting material used was a deposition The barium sulfate has a crystal size d5o of 26 nm. To make this composite, the barium sulfate was first dispersed in ethylene glycol (EG) with a bead mill and then passed through a 丨μπ1 filter. This 30% suspension was then used in the polycondensation to produce PET pellets having 2.5 weights of lanthanum/niobium sulfate. The composite and a PET green polymer were used to produce a test body using an injection molding machine for tensile and bending tests. The specimen was then treated at 23 C and 50% relative humidity for 9 hours. The results of the tensile test (according to DIN EN ISO 527) and the bending test (according to DIN ΕΝ ISO 178) are shown in Tables 2 and 3. With the green polymer phase 26 200909500 乂 乂 tensile modulus and rupture tensile improvement. And the bending modulus and bending strength can be improved by using &amp; acid lock. In addition, the singularity is that the Vicat softening temperature is significantly increased from the 78 of the raw &amp; compound to the 1 68 °C of the nanocomposite. Table 2 · Tensile test results of composites composed of PET and barium sulfate according to Example 3 __ Tensile modulus "Mpal rupture tensile" %1 PET pure polymer from PET and 2 · 5% by weight sulfuric acid lock - 2443 7.8 Composite composed 3068 0.4 Table 3: According to the results of the example test, the composite of PET and barium sulphate

2719 by PET A 2.5 weight. / 〇 〇 锁 锁 〔 〔 实例 实例 实例 实例 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Secret ^ ^ yari fatty acid (stearic acid Edensor ST 1 modified. For example, this ancient u organically modified barium sulphate can be manufactured by the following method will be 9Kg of the sinking double k. Then, it is mixed with 1 〇27 200909500 wt% stearic acid (Edenor ST 19) in a Diosna mixer, in which stearic acid is melted due to heat generation of the product. The resulting product is then re-milled with a pin mill. Surface modified barium sulphate and a commercially available polyamine 6 (Ultramide B2715, BASF) first used a melt extrusion to make a 20% by weight main batch. In the second extrusion step, the main batch was diluted to sulfuric acid. The cerium concentration is 2.0% by weight and 7.4% by weight. The shoulder bar is manufactured using an injection molding machine for tensile testing (according to DIN EN ISO 527), and the small rod is manufactured for bending test (according to DIN ΕΝ ISO 1 78). The test body was at 23 ° C and 50% relative humidity After treatment for 72 hours, in this composite, compared with the green polymer, the tensile strength and tensile modulus are significantly increased, and the fracture stretch is reduced. And the bending property (bending modulus and bending strength) can be changed by using the surface. The quality of barium sulphate is significantly improved (see Table 5). The impact toughness (according to DIN EN ISO 179) is improved only when 2% by weight of surface-modified barium sulphate is used, compared to pure polyamide 6. Table 4 : Tensile test results of composites composed of PA6 and surface-modified barium sulfate according to Example 4 Sample particle content Tensile strength cracking Tensile tensile modulus Weight % TMPal Γ%1 [MPal PA6 Ultramid B2715 (BASF) 0 67.99 108.63 2464.7 Nanocomposite consisting of PA and surface modified barium sulphate 2 73.7 22.6 2944.4 Nanocomposite consisting of PA and surface modified barium sulphate 7.4 75.7 8.3 3038.4 28 200909500 Table 5: Example 4 Results of bending test of composite composed of PA6 and surface-modified barium sulfate. Sample name Particle content Bending strength Bending modulus Bending toughness % [MPal [MPal 『KJ/m2l PA6 Ultramid B2715 (BASF) 0 87.5 1920 92.24 Nanocomposite consisting of PA6 and surface modified barium sulphate 2 91.0 2057.6 99.6 Nanocomposite consisting of PA6 and surface modified barium sulphate 7.4 94.3 2148.7 40.2 [Simplified illustration] Figure 1 Example The fracture toughness of a composite of 1, which is a function of the degree of filling. Figure 2 is the flexural modulus of the composite of Example 1, which is a function of the degree of filling. Figure 3 is the flexural strength of the composite of Example 1, which is a function of the degree of filling. [Main component symbol description] None 29

Claims (1)

200909500 X. Patent application scope: A kind of compound, which is dispersed by filler and pigment in - φ gentleman, # 母母母' ” characteristics: the complex contains barium sulfate, plastic 脒, 丝一一王夕Thermoplastic ^ A power plastic and / or an epoxy grease, - the surname a and then the barium sulfate, the mouth size of the day is less than 350 nm, and should be less than 2 〇〇 too., not wood 'you * should ~50 nm, and the barium sulfate can be modified with inorganic and/or organic. Eight surface 2. The composite of claim 1 wherein: the thermoplastic used is at least one polyester, one poly Amine, a bismuth, a polyethylene, a polypropylene, a polyphenylene, a copolymer thereof and/or a mixture thereof, a polycarboxylate, a PMMA and/or a polyvinyl chloride, or at least two such thermoplastics. The mixture is used as a thermoplastic. 3. The composite of claim 1 or 2, wherein: the selected high-power plastic is at least one year heavy PTFE, chlorine thermoplastic (eg FEP, PFA, etc.), PVDF a polysulfone (eg pEp, PSU, P) PSU, etc.), polysodium amide, a liquid crystal polymer and/or a polyetheretherketone, or a mixture of two of these high-power plastics is used as a high-power plastic. The composite of item 2, wherein: 5 ha complex contains 12 to 99.8% by weight of thermoplastic plastic, 〇丨~(9) 5% by weight of barium sulfate, 0 to 80% by weight of mineral filler and/or glass fiber, 0.06 ~10% by weight of antioxidant, 〇~〇2〇% by weight of organic metal in addition to living biocide, 〇~2.0% by weight of program additives (for example, dispersion aid, adhesion agent), 0 to 10% by weight of pigment and enamel ~4〇% by weight of flame retardant (Example 30 200909500 such as aluminum hydroxide, antimony trioxide, argon oxide) 5. As claimed in the patent scope of the scope of the compound of item 2 or 2, where: to. Contains 12~99% by weight of high-power plastic, 〇"~6〇 里 馼钡 馼钡, 〇~80% by weight mineral filler and / or glass fiber, 〇 5. 〇 ΐ 程序 % program additives (such as dispersion subsidies) , adhesion agent), 〇 ~ 10% by weight of pigment. 6. The composite of claim 1 or 2, wherein: the composite contains 20 to 99% by weight of epoxy resin, palpitations ~ (9) weight / o & S 钡 0, 0 〜 8 〇 weight% minerals Filler and / or fiberglass, 〇 ~ 1 〇 reset % program addition, 〇 ~ 1 〇 wt% pigment and 〇 ~ 4 〇 wt% aluminum hydroxide. 7. The composite of claim 1 or 2, wherein: the ratio of barium sulfate in the composite is 0.1 to 60% by weight, and preferably 0.5 to 30% by weight, particularly preferably 1 to 0 to 20% by weight. %. 8. The composite of claim 1 or 2, wherein: the barium sulfate is surface treated with at least one inorganic compound. 9_ The composite of claim 7, wherein: the weight ratio of the inorganic compound (relative to BaS04) is 0.1 to 50.0% by weight, and preferably 1.0 to 10.0% by weight. 10. The composite of claim 8 wherein: the inorganic compound is selected from the group consisting of water soluble aluminum, strontium, barium, calcium, strontium, chlorine, cobalt, iron, phosphorus, carbon, manganese, oxygen. a compound or salt of sulfur, strontium, nitrogen, strontium, hunger, zinc, tin and/or strontium. 11. A composite as claimed in claim 8 wherein: 31 200909500 the BaS〇4 particles are additionally modified with at least one decane or a plurality of additions to the surface modification of the inorganic compound. 1 2. The composite of claim 11 wherein: the zephyr is an alkoxyalkyl decane. 13. The composite of claim 12, wherein: the alkoxyalkylnonane is selected from the group consisting of: octyltriethoxydecane, r-methylpropenylpropyltrimethoxydecane, Τ_glycidylpropyltrimethoxy decane, aminopropyltriethyl decane, τ-aminopropyltrimethoxy decane, isocyanate propyl triethoxy decane, vinyl trimethoxy Decane and/or chlorinated decane, such as r-aminopropyl sesquiquinoxaline (GE). 14. The composite of claim 1 or 2, wherein: the primary particle size of the BaS〇4 particles is less than or equal to 〇, and is preferably 0.05 〇.〇〇5μηι. I5. The composite of claim 1 or 2, wherein: the barium sulfate is surface modified with at least one organic compound. 16. The composite of claim 15 which is selected from the group consisting of polyether, decane, polyoxyalkylene polycarboxylic acid, fatty acid, polyethylene glycol, polyester, polyamine , or a polyalcohol, an organic phosphonic acid, a titanate, a zirconate, an alkyl and/or an aryl sulfonate, an alkyl and/or aryl sulfate, an alkyl and/or an aryl phosphate, or A mixture of at least two compounds. 1 7. The composite of claim 5, wherein: the organic compound is selected from the group consisting of alkyl sulfonate, polyethylene 32 200909500 sodium, N-alkyl sodium , polystyrene sodium, 12 sodium sulphate sodium, laurel sodium sulphate, sodium sulphate sulphate, sulphate sulphate, triethanol ammonium lauryl sulphate, monoethyl monobenzyl phosphate, Peroxidized octyl sulphate, 12-mist-1_12 calcined acid, 1 〇 _ 经 癸 癸 癸 癸 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Sodium hexadecane sulfonate, 16-hexadecane (1), sodium sulphate, octadecyl alcohol sulfate, oleic acid sulfate, 9,10-dihydroxystearic acid, isostearic acid, stearic acid An acid, oleic acid, or a mixture of at least two such compounds. 1 8. The composite of claim 15 wherein: the average particle size of the sulfuric acid lock is preferably ^^=1 nm~1〇〇N, and preferably d50=l nm~1μπι, especially suitable d5 〇 = 5 nm ~ 〇 5 μιη. 19_ The composite of claim 15 wherein: the primary particle size preferably has a logarithmic particle size distribution, wherein the value is ~5000 nm, and preferably d=1~i〇〇〇N, especially Preferably, d = 5 to 5 nanometers, and the geometric standard deviation of the logarithmic particle size distribution is &lt;15, and preferably σ§ &lt; 1.4. (10) A composite according to claim 15 wherein: n (tetra) functional group of the money derivative or functional group ♦ is selected after firing: butyl triethoxy sulphur, methoxy or: alkenyl Oxypropyl methoxy Wei, Qian, methacrylate, 7-aminopropyl triethoxy, 7 glyceryloxypropyl trimethoxy decane, vinyl trimethoxy decane 2, 7 a mixture of isopropyl isocyanate and triethoxy. At least two such compounds of the formula 33 200909500 21· A method for producing a composite of claim 1 wherein: a primary batch is produced from the barium sulfate and a portion of the green polymer, and The main batch was diluted with a green polymer to obtain a dispersion. 22. The method of claim 21, wherein: a primary batch is produced from the barium sulfate and a portion of the green polymer, and the composite is obtained by diluting the primary batch with the green polymer, Wherein the main batch contains 5 to 80% by weight, and preferably 15 to 6% by weight of barium sulfate. 23. The method of claim 21, wherein: Λ the main approver and the other components of the genre are mixed in one or several steps, and then the work is dispersed. 24. The method of claim 21, wherein: the acid-slurry lock is first processed and dispersed in an organic substance, particularly in an amine, poly: leaven, phenelzine, carbamide and its molded body, vinyl vinegar Resin, polyester resin or 矽力康 resin. 25. The method of claim 18, wherein: the complex is reacted with an organic substance that acts on barium sulfate. The organic matter is used as a starting material for the preparation of bismuth. For example, the method of the 21st working page of the patent application, the _·· the strontium sulphate utilizes the conventional dispersion method ‘Quality, the other is β, you m knife in the main batch or An organic matter: special use of melt extruder, dissolver, mill, bead mill, bead mill, dip, as widely as the scope of patent application ... square or kneading machine. The dispersion of bismuth should be in the dipping mill or beads The invention is carried out in a grain mill. 34 200909500 28. The method of claim 15, wherein: the 5 sulphuric acid lock dispersion operation is carried out in a bead mill, wherein the diameter of the beads used is d &lt; 1.5 mm 'and preferably d &lt; 1. 〇mm, especially d&lt;〇_3mni. ^ . The application of the composite of claim 1 is for the use of = starting materials for the manufacture of molded bodies, semi-finished products, films or fibers, in particular It is ^ 'out of the formed parts, blow molding or fiber. Car Μ: two please: the application of the composite of the scope of the first item' is used for gears, and, in the space navigation field, 'particularly sliding Bearing, 3 α and piston cladding. Please apply the compound of the first item of the patent scope, and use the sputum and Shengsheng 1 series for the concrete prosthesis &amp; 'adhesive, industrial floor, concrete cladding, metal tube clearing and cleaning , anti-corrosion coating, cast electrical components or other items:, pieces... as a carrier material in plastics' or wood storage: the seal of the lips will be sealed ten- and two-type: